Design principle of single-atom catalysts for sulfur reduction reaction—interplay between coordination patterns and transition metals  

用于硫还原反应的单原子催化剂的设计原则—配位模式与过渡金属的相互作用

作　　者：Wentao Zhang Gaoshang Zhang Zhaotian Xie Xinming Zhang Jiabin Ma Ziyao Gao Kuang Yu Lele Peng 张文涛;张高尚;谢昭天;张新明;马家宾;高子耀;余旷;彭乐乐(Tsinghua Shenzhen International Graduate School,Tsinghua University,Shenzhen 518055,China;School of Materials Science and Engineering,Tsinghua University,Beijing 100084,China)

机构地区：[1]Tsinghua Shenzhen International Graduate School,Tsinghua University,Shenzhen 518055,China [2]School of Materials Science and Engineering,Tsinghua University,Beijing 100084,China

出　　处：《Science China Materials》2024年第10期3215-3224,共10页中国科学（材料科学）（英文版）

基　　金：supported by the Scientific Research Start-up Funds of Tsinghua SIGS(QD2021018C to Peng L);the National Natural Science Foundation of China(20231710015 and 22209096 to Peng L);GuangDong Basic and Applied Basic Research Foundation(2023A1515010059 to Peng L);Shenzhen Fundamental Research Program(JCYJ20220530143003008 to Peng L);Shenzhen Science and Technology Program(ZDSYS20230626091100001)。

摘　　要：The polysulfide shuttling effect is the primary bottleneck restricting the industrial application of Li-S batteries,and the electrocatalytic sulfur reduction reaction(SRR)has emerged as an effective solution.Carbon-based singleatom catalysts(SACs),which promotes SRR,show great potential in inhibiting the shuttling effect of polysulfides.Meanwhile,the optimization and rational design of such catalysts requires a deep understanding to the fundamental SRR mechanism and remains highly nontrivial.In this work,we construct a comprehensive database of carbon-based SACs,covering different coordination patterns,heteroatoms,and transition metals.The SRR activities are determined using density functional theory calculations,revealing a synergistic effect between the p orbital of the heteroatom and the d orbital of the transition metal.This interplay underscores the critical importance of the coordination environment for SRR under the ortho-P_(2)C_(2)structure.Regardless of the transition metal type,the ortho-P_(2)C_(2)coordination pattern significantly enhances the SRR performance of SACs,surpassing the widely reported N_(3)C_(1)and N_(4)coordinated graphene-based SACs.Furthermore,heteroatoms with ortho-P_(2)C_(2)may exhibit SRR activity.In a word,by using this comprehensive dataset and data-driven framework,we propose a promising novel class of coordination structure(ortho-P_(2)C_(2)structure)and neglected design principle.多硫化物穿梭是制约锂硫电池产业化的主要瓶颈,电催化硫还原(SRR)被认为是一种有效解决方案.碳基单原子催化剂(SACs)能够显著促进SRR,同时,这种催化剂的优化和理性设计需要对SRR基本机制有深入了解.在这项工作中,构建了涵盖不同配位模式、杂原子和过渡金属类型的全面的碳基SACs数据库.利用密度泛函理论计算了相应SACs的SRR活性,揭示了杂原子p轨道和过渡金属d轨道之间的协同效应.这种相互作用强调了配位环境对SRR活性的极端重要性.无论过渡金属类型如何,ortho-P_(2)C_(2)配位模式均显著提高SACs的SRR性能,使得相应的SRR性能远远超过广泛报道的N_(3)C_(1)和N_(4)配位SACs.此外,具有ortho-P_(2)C_(2)结构的杂原子可能表现出SRR活性.总之,提出了一类有前途的新型配位结构(ortho-P_(2)C_(2))和被忽略的设计原则.

关 键 词：single-atom catalysts ortho-P doped structure abinitio calculations machine learning sulfur reduction reaction 

分 类 号：O643.36[理学—物理化学] TM912[理学—化学]